Detergent compositions

ABSTRACT

There is provided a detergent composition containing an amylase enzyme and a builder system comprising an aluminosilicate zeolite, a crystalline layered silicate and most preferably an organic polymeric compound wherein the weight ratio of said crytalline layered silicate to said amylase enzyme (120 KNU/gram activity basis) is from 7:1 to 20:1. In one preferred aspect the detergent composition contains a bleaching system capable of providing delayed release of an organic peroxyacid to a wash solution.

This invention relates to detergent compositions particularly suitable for use in a laundry washing method containing an amylase enzyme in combination with a builder system.

Builder systems are commonly used in detergent compositions for their stain removal and water softening capabilities. Composite builder systems comprising more than one builder compound are often used, including those comprising aluminosilicate zeolite, crystalline layered silicate and optionally organic polymeric compound.

The satisfactory removal of particular soils/stains such as blood, spinach, ink, chocolate and tomato sauce from soiled/stained substrates is a challenge to the formulator of a detergent composition for use in a washing method such as a laundry or machine dishwashing method. Enzymes are commonly employed in detergent compositions to aid the removal of such soils/stains from substrates in the wash.

A problem encountered with the use of enzymes as components of detergents is that enzyme activity in the wash is sensitive to the presence of other chemical components in the wash solution. In particular, it has been established that a certain level of hardness ions, particularly calcium ions is necssary to ensure effective enzyme action. Without wishing to be bound by theory, it is believed that the formation of hardness ion-enzyme associations are necessary to ensure this enzyme action. Amylolytic enzymes have been found to be especially sensitive to hardness ion levels.

It has been found that a problem can be encountered with amylase-containing detergents when certain builder systems, especially those comprising aluminosilicate zeolite, crystalline layered silicate and optionally organic polymeric compound, are present in the detergent composition, such that on introduction of the detergent to a wash solution both the amylase and the builder system are commonly present in the wash solution. The builder system is believed to prevent the formation of, or to disrupt, the hardness ion-enzyme associations which are necessary for effective enzyme action. Reduced enzymatic soil/stain removal capability has thus been observed.

The Applicants have now however, found that for a detergent composition containing both an amylase enzyme and a builder system comprising aluminosilicate zeolite, crystalline layered silicate and preferably organic polymeric compound enhanced stain/soil removal, particularly on enzymatically sensitive stains/soils, may be obtained if the weight ratio of layered silicate to amylase (120 KNU/g activity basis) is from 7:1 to 20:1.

The problem of enzyme degradation has been only partially recognized in the art, but no specific recognition of the importance of enzyme-calcium associations for effective enzyme performance appears to have been made. For example, in U.S. Pat. No. 4,176,079 A it is stated that `enzymes tend to degrade and become inactive in the highly alkaline detergent composition environment`, and that enzymes may be `subject to interference and attack from incompatible components such as phosphates, in the washing solution`. Thus, the problem of enzyme degradation is linked to high pH and/or phosphates, but not specifically to builder systems of the type herein provided.

EP-A-552,287 describes a phosphate-free builder combination containing zeolite in quantities of 60 to 96% by weight, crystalline layer silicate corresponding to formula NaMSi_(x) O_(2x+1).yH₂ O, in which M is sodium or hydrogen, x is a number of 0 to 20, in quantities of 2 to 25% by weight and polymeric polycarboxylate in quantities of 2 to 16% by weight and, optionally, phosphonate, the ratio by weight of crystalline layer silicates to polymeric polycarboxylates being 3:1 to 1:3. Enzymes are generally described as optional components.

SUMMARY OF THE INVENTION

According to the present invention there is provided a detergent composition containing

(a) an amylase enzyme; and

(b) a builder system comprising

(i) an aluminosilicate zeolite; and

(ii) a crystalline layered silicate;

wherein the weight ratio of said crystalline layered silicate to said amylase enzyme (120 KNU/gram activity basis) is from 7:1 to 20:1.

Most preferably, the builder system also contains an organic polymeric compound.

Amylase

An essential component of the compositions is an amylase enzyme, that is to say an enzyme having amylolytic activity.

The level of amylase enzyme present in the detergent composition is proportionate to the level of crystalline layered silicate builder present therein. The weight ratio of crystalline layered silicate to amylase enzyme (on a 120 KNU/g (Kilo Novo Units/gram) activity basis) is from 7:1 to 20:1, preferably from 8:1 to 18:1, most preferably from 10:1 to 16:1.

Typically, the amylase enzyme will be incorporated into the detergent compositions at a level of from 0.1% to 5%, preferably from 0.2% to 3%, more preferably from 0.3% to 2%, most preferably from 0.4% to 1.5% by weight of the composition, on a 120 KNU/g (Kilo Novo Units/gram) activity basis.

The units of `Kilo Novo Units/gram (KNU/g)` are a well known means of defining amylolytic enzyme activity and are described in GB-1,269,839 A (Novo). In more detail, 1 KNU is the amount of enzyme which breaks down 5.25 grams of starch (Merck, Amylum Solubile Erg. B.6, Batch 9947275) per hour in the method described in GB-1,269,839 A, which has the following standard conditions:

Substrate Soluble starch

Calcium content in solvent 0.0043 M

Reaction time 7-20 minutes

Temperature 37° C.

pH 5.6

The amylase enzyme may be fungal or bacterial in origin. Amylases obtained by chemical or genetic manipulation of fungal or bacterial derived strains are also useful herein. The amylase enzyme is preferably an α-amylase.

Preferred amylases include, for example, α-amylases obtained from a special strain of B. licheniformis, described in more detail in GB-1,269,839 A. Reported deposit numbers for B. licheniformis strains capable of producing α-amylases include NCIB 8061, NCIB 8059, ATCC 6634, ATCC 6598, ATCC 11945, ATCC 8480 and ATCC 9945a.

Preferred commercially available α-amylases include for example, those sold under the tradename Rapidase and Maxamyl by Gist-Brocades; those sold under the tradename Taka-Therm L-340 by Miles Laboratories, Elkhart, Ind.; those sold under the tradename Rohalase AT by Rohm and Haas, West Philadelphia, Pa.; and those sold under the tradenames Termamyl 60T and 120T, Fungamyl and BAN by Novo Industries A/S.

In a preferred aspect, the amylases have been designed to have improved stability, particularly having improved stability to oxidation, for example in a bleaching environment, and improved thermal stability. Stability can be measured using any of the technical tests known in the art including those referred to in WO 94/02597 A. Stability-enhanced amylases are commercially available from Novo Industries A/S or from Genencor International.

Highly preferred amylases with enhanced oxidative stability are derived using site-directed mutagenesis from one or more of the Baccillus amylases, especialy the Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Preferred amylases of this type are described in WO 94/02597 A, and comprise a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis α-amylase, sold under the tradename Termamyl, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus.

Other preferred amylases having enhanced oxidative stability, derived from B. licheniformis NCIB806, are described by Genencor International in a paper entitled "Oxidatively Resistant α-Amylases" which was presented at the 207th American Chemical Society National Meeting, Mar. 13-17 1994, by C. Mitchinson. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant.

Other preferred amylases having enhanced oxidative stability include those described in WO 94/18314 A (Genencor International) and WO 94/02597 A (Novo). Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other enzyme modifications are acceptable including those described in WO 95/09909 A (Novo).

It will be appreciated that enzymes for incorporation into solid detergent compositions are generally sold commercially as enzyme prills containing active enzyme supported on a variety of inert host materials, which for example, can include alkali metal sulfates, carbonates and silicates.

Optionally, organic binder materials are also incorporated. In a preferred aspect, the calcium content of these enzyme prills is minimzed to ensure good in-product storage stability of the enzyme.

Builder system

The detergent compositions contain as an essential component a builder system comprising an aluminosilicate zeolite and a crystalline layered silicate. Optionally other builders, particularly organic polymeric compounds, may also be present.

By builder herein it is meant a component capable of controlling the level of hardness ions, that is Ca²⁺ and Mg²⁺, in a wash solution. Said control can for example, occur by chelation or sequestration of the hardness ions, or alternatively by ion-exchange mechanisms.

The builder system is typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the detergent composition.

Aluminosilicate zeolite builder

Essentially any known aluminosilicate zeolite builders are envisaged for use herein. The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof.

Suitable aluminosilicate zeolite builders herein include those having the unit cell formula Na_(z) [(AlO₂)_(z) (SiO₂)y]. XH₂ O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

Zeolite A has the formula

    Na.sub.12 [AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ]. xH.sub.2 O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na₈₆ [(AlO₂)₈₆ (SiO₂)₁₀₆ ]. 276 H₂ O.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.

The aluminosilicate zeolite builder is preferably present in the builder system at a level of from 40% to 98%, more preferably from 50% to 95%, most preferably from 60% to 90% of active aluminosilicate zeolite by weight of the builder system. By `active aluminosilicate zeolite by weight` it is meant herein that the weight of aluminosilicate zeolite is expressed on an active basis i.e. in the absence of any water of crystallization.

Crystalline layered silicate builder

Essentially any crystalline layered silicate builders are suitable herein. Preferred crystalline layered sodium silicates herein have the general formula

    NaMSi.sub.x O.sub.2x+1. yH.sub.2 O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. The most preferred material is δ-Na₂ Si₂ 0₅, available from Hoechst AG as NaSKS-6.

The crystalline layered sodium silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble ionisable material. The solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.

The crystalline layered silicate builder is preferably present in the builder system at a level of from 1% to 35%, more preferably from 3% to 30%, most preferably from 5% to 25% crystalline layered silicate by weight of the builder system.

Optional builders.

Suitable optional builder compounds include the organic polymeric compounds, water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates, silicates and mixtures of any of the foregoing.

Suitable carboxylate or polycarboxylate builder are momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid (pK(Ca) at pH 10.5=1.20), malonic acid (pK(Ca) at pH 10.5=1.51), (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran--cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran--cis--dicarboxylates, 2,2,5,5-tetrahydrofuran--tetracarboxylates, 1,2,3,4,5,6-hexane--hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. Citrate has a pK(Ca) at pH 10.5 of 3.50.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used as optional builder components but are not preferred at wash conditions less that about 50° C., especially less than about 40° C.

Carbonate builders are also suitable optional builders including for example, the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on Nov. 15, 1973.

Specific examples of water-soluble phosphate builders, suitable as optional builders herein, are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Suitable optional builder herein also inlcude silicates includeing the water soluble sodium silicates with an SiO₂ :Na₂ O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO₂ : Na₂ O ratio of 2.0 is the most preferred silicate.

Other suitable optional builders herein are the organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates. Preferred among the above species are diethylene triamine penta (methylene phosphonate) which has a pK(Ca) of about 9.95 at pH 10.5, ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, whose pK(Ca) is 6.84 at pH 10.5.

Ethylenediamine tetraacetic acid (EDTA) is also a suitable optional builder herein.

For clarity it is noted that builders which are acidic in nature, having for example phosphoric acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably any salts/complexes are water soluble.

Organic polymeric compound

Any organic polymeric compound capable of acting as a builder is suitable herein as a preferred optional component of the builder system. The organic polymeric compound may also function as a dispersant, anti-redeposition or soil suspension when incorporated into the detergent compositions.

Preferred organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polymers containing acrylic acid monomer units. Preferred examples include polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.

Other suitable organic polymeric compounds include the polymers of acrylamide and acrylate having a molecular weight of from 3,000 to 100,000, and the acrylate/fumarate copolymers having a molecular weight of from 2,000 to 80,000.

The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-35 1629.

Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000 are also suitable herein.

Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.

Organic polymeric compound is typically incorporated in the builder system at a level of from 0.1% to 20%, preferably from 1% to 16%, most preferably from 2% to 12% organic polymeric compound by weight of the builder system.

Additional detergent components

The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.

The compositions of the invention may for example, be formulated as hand and machine laundry detergent compositions, including laundry additive compositions and compositions suitable for use in the pretreatment of stained fabrics and machine dishwashing compositions.

When formulated as compositions suitable for use in a machine washing method, eg: machine laundry and machine dishwashing methods, the compositions of the invention preferably contain one or more additional detergent components selected from additional enzymes, enzyme stabilizing systems, surfactants, bleaches, heavy metal ion sequestrants, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain, as additional detergent components, softening agents.

Additional enzymes

Suitable additional enzymes include the commercially available lipases, neutral and alkaline proteases, cellulases, pectinases, lactases and peroxidases, that is enzymes having lipolytic, proteolytic, cellulolytic, pectolytic, lactolytic and peroxidolytic activity respectively, conventionally incorporated into detergent compositions. Suitable enzymes are discussed in U.S. Pat. Nos. 3,519,570 and 3,533,139.

Protease enzymes are especially preferred as the enzyme component. Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.

Lipolytic enzyme (lipase) which are also preferred may be present at levels of active lipolytic enzyme of from 0.0001% to 4% active enzyme by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.

The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.

A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus orvza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Pat. No. 4,810,414, Huge-Jensen et al, issued Mar. 7, 1989.

Enzyme Stabilizing System

Preferred enzyme-containing compositions herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%,most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, and mixtures thereof. Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

The compositions herein may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during washing is usually large; accordingly, enzyme stability in-use can be problematic.

Suitable chlorine scavenger anions are widely available, and are illustrated by salts containing ammonium cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used. Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof can be used if desired.

Surfactant

The detergent compositions of the invention may contain as an optional detergent component a surfactant selected from anionic, cationic, nonionic ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

The surfactant is typically present at a level of from 0.1% to 60% by weight. More preferred levels of incorporation of surfactant are from 1% to 35% by weight, most preferably from 1% to 20% by weight. The surfactant is preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S. Pat. No. 4,259,217 issued to Murphy on Mar. 31, 1981.

Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.

Anionic surfactant

Essentially any anionic surfactants useful for detersive purposes can be included in the compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C₁₂ -C₁₈ monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C₆ -C₁₄ diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C₅ -C₁₇ acyl--N--(C₁ -C₄ alkyl) and --N--(C₁ -C₂ hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C₆ -C₁₈ alkyl sulfates which have been ethoxylated with from about 0.5 to about 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C₆ -C₁₈ alkyl sulfate which has been ethoxylated with from about 0.5 to about 20, preferably from about 0.5 to about 5, moles of ethylene oxide per molecule.

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of C₅ -C₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C₆ -C₂₂ primary or secondary alkane sulfonates, C₆ -C₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactant

Anionic carboxylate surfactants suitable for use herein include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps (`alkyl carboxyls`), especially certain secondary soaps as described herein.

Preferred alkyl ethoxy carboxylates for use herein include those with the formula RO(CH₂ CH₂ O)_(x) CH₂ C00⁻ M⁺ wherein R is a C₆ to C18 alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than about 20%, and the amount of material where x is greater than 7, is less than about 25%, the average x is from about 2 to 4 when the average R is C₁₃ or less, and the average x is from about 3 to 10 when the average R is greater than C₁₃, and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions. The preferred alkyl ethoxy carboxylates are those where R is a C₁₂ to C18 alkyl group.

Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include those having the formula RO--(CHR₁ --CHR₂ --O)--R₃ wherein R is a C₆ to C₁₈ alkyl group, x is from 1 to 25, R₁ and R₂ are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, wherein at least one R₁ or R₂ is a succinic acid radical or hydroxysuccinic acid radical, and R₃ is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Anionic secondary soap surfactant

Preferred soap surfactants are secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. The secondary carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexyl carboxylates. The secondary soap surfactants should preferably contain no ether linkages, no ester linkages and no hydroxyl groups. There should preferably be no nitrogen atoms in the head-group (amphiphilic portion). The secondary soap surfactants usually contain 11-15 total carbon atoms, although slightly more (e.g., up to 16) can be tolerated, e.g. p-octyl benzoic acid.

The following general structures further illustrate some of the preferred secondary soap surfactants:

A. A highly preferred class of secondary soaps comprises the secondary carboxyl materials of the formula R³ CH(R⁴)COOM, wherein R³ is CH₃ (CH₂)x and R⁴ is CH₃ (CH₂)y, wherein y can be O or an integer from 1 to 4, x is an integer from 4 to 10 and the sum of (x+y) is 6-10, preferably 7-9, most preferably 8.

B. Another preferred class of secondary soaps comprises those carboxyl compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit, i.e., secondary soaps of the formula R⁵ --R⁶ --COOM, wherein R⁵ is C⁷ -C¹⁰, preferably C⁸ -C⁹, alkyl or alkenyl and R⁶ is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note: R⁵ can be in the ortho, meta or para position relative to the carboxyl on the ring.)

C. Still another preferred class of secondary soaps comprises secondary carboxyl compounds of the formula CH₃ (CHR)_(k) --(CH₂)_(m) --(CHR)_(n) --CH(COOM)(CHR)_(o) --(CH₂)_(p) --(CHR)_(q) --CH₃, wherein each R is C₁ -C₄ alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the total number of carbon atoms (including the carboxylate) is in the range of 10 to 18.

In each of the above formulas A, B and C, the species M can be any suitable, especially water-solubilizing, counterion.

Especially preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R--CON (R¹) CH₂ COOM, wherein R is a C₅ -C₁₇ linear or branched alkyl or alkenyl group, R¹ is a C₁ -C₄ alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleyl methyl sarcosinates in the form of their sodium salts.

Nonionic surfactant

Essentially any anionic surfactants useful for detersive purposes can be included in the compositions. Exemplary, non-limiting classes of useful nonionic surfactants are listed below.

Nonionic polyhydroxy fatty acid amide surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R² CONR¹ Z wherein: R1 is H, C₁ -C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C1-C4 alkyl, more preferably C₁ or C₂ alkyl, most preferably C₁ alkyl (i.e., methyl); and R₂ is a C₅ -C₃₁ hydrocarbyl, preferably straight-chain C₅ -C₁₉ alkyl or alkenyl, more preferably straight-chain C₉ -C₁₇ alkyl or alkenyl, most preferably straight-chain C₁₁ -C₁₇ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic condensates of alkyl phenols

The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 18 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.

Nonionic ethoxylated alcohol surfactant

The alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.

Nonionic ethoxylated/propoxylated fatty alcohol surfactant

The ethoxylated C₆ -C₁₈ fatty alcohols and C₆ -C₁₈ mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble. Preferably the ethoxylated fatty alcohols are the C₁₀ -C₁₈ ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C₁₂ -C₁₈ ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.

Nonionic EO/PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Examples of compounds of this type include certain of the commercially-available Pluronic™ surfactants, marketed by BASF.

Nonionic EO condensation products with propylene oxide/ethylene diamine adducts

The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic™ compounds, marketed by BASF.

Nonionic alkylpolysaccharide surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units.

The preferred alkylpolyglycosides have the formula

    R.sup.2 O(C.sub.n H.sub.2n O)t(glycosyl).sub.x

wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t is from 0 to 10, preferably 0, and X is from 1.3 to 8, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose.

Nonionic fatty acid amide surfactant

Fatty acid amide surfactants suitable for use herein are those having the formula: R⁶ CON(R⁷)₂ wherein R⁶ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R⁷ is selected from the group consisting of hydrogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, and --(C₂ H₄ O)_(x) H, where x is in the range of from 1 to 3.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

A suitable example of an alkyl aphodicarboxylic acid for use herein is Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, N.J.

Amine Oxide surfactant

Amine oxides useful herein include those compounds having the formula R³ (OR⁴)_(x) N⁰ (R⁵)₂ wherein R³ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 18 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R⁵ is an alkyl or hydyroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable 1, ethylene oxide groups. The R⁵ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀ -C18 alkyl dimethyl amine oxides and C₈ -C₁₈ alkoxy ethyl dihydroxyethyl amine oxides. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, tallow dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. Preferred are C₁₀ -C₁₈ alkyl dimethylamine oxide, and C₁₀ -₁₈ acylamido alkyl dimethylamine oxide.

Zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Betaine surfactant

The betaines useful herein are those compounds having the formula R(R')₂ N⁺ R² COO-- wherein R is a C₆ -C₁₈ hydrocarbyl group, preferably a C₁₀ -C₁₆ alkyl group or C₁₀₋₁₆ acylamido alkyl group, each R¹ is typically C₁ -C₃ alkyl, preferably methyl,m and R² is a C₁ -C₅ hydrocarbyl group, preferably a C₁ -C₃ alkylene group, more preferably a C₁ -C₂ alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C₁₂₋₁₄ acylamidopropylbetaine; C₈₋₁₄ acylamidohexyldiethyl betaine; 4[C₁₄₋₁₆ acylmethylamidodiethylammonio]-1-carboxybutane; C₁₆₋₁₈ acylamidodimethylbetaine; C₁₂₋₁₆ acylamidopentanediethyl-betaine; [C₁₂₋₁₆ acylmethylamidodimethylbetaine. Preferred betaines are C₁₂₋₁₈ dimethyl-ammonio hexanoate and the C₁₀₋₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Sultaine surfactant

The sultaines useful herein are those compounds having the formula (R(R¹)₂ N⁺ R² SO₃ -- wherein R is a C₆ -C₁₈ hydrocarbyl group, preferably a C₁₀ -C₁₆ alkyl group, more preferably a C₁₂ -C₁₃ alkyl group, each R¹ is typically C₁ -C₃ alkyl, preferably methyl, and R² is a C₁ -C₆ hydrocarbyl group, preferably a C₁ -C₃ alkylene or, preferably, hydroxyalkylene group.

Ampholytic surfactant

Ampholytic surfactants can be incorporated into the detergent compositions herein. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.

Cationic surfactants

Cationic surfactants can also be used in the detergent compositions herein. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C₆ -C₁₆, preferably C₆ -C₁₀ N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Heavy metal ion sequestrant

The detergent compositions of the invention may contain as a preferred optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.

Heavy metal ion sequestrants, which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably any salts/complexes are water soluble. The molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1:1.

Suitable heavy metal ion sequestrants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.

Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof. Examples of such preferred sodium salts of EDDS include Na₂ EDDS and Na₃ EDDS. Examples of such preferred magnesium complexes of EDDS include MgEDDS and Mg₂ EDDS. EDDS is also a good calcium chelating agent, having a pK(Ca) at pH 10.5 of 4.96.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.

The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS) is also suitable.

Organic peroxyacid bleaching system

According to one aspect of the present invention the detergent compositions contain an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.

Inorganic perhydrate bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.

Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBO₂ H₂ O₂ or the tetrahydrate NaBO₂ H₂ O₂.3H₂ O.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na₂ CO₃.3H₂ O₂, and is available commercially as a crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.

Peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as ##STR1## where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is ##STR2##

Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N-- or O--acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Leaving groups

The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of: ##STR3## and mixtures thereof, wherein R¹ is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R³ is an alkyl chain containing from 1 to 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizing group. Any of R¹, R³ and R⁴ may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

The preferred solubilizing groups are --SO₃ ⁻ M⁺, --CO₂ ⁻ M⁺, --SO₄ ⁻ M⁺, --N⁺ (R³)₄ X⁻ and O←N(R³)₃ and most preferably --SO₃ ⁻ M⁺ and --CO₂ ⁻ M⁺ wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkyl percarboxylic acid bleach precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N¹ N¹ tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

Amide substituted alkyl peroxyacid precursors

Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae: ##STR4## wherein R¹ is an alkyl group with from 1 to 14 carbon atoms, R² is an alkylene group containing from 1 to 14 carbon atoms, and R⁵ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic peroxyacid precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.

Cationic peroxyacid precursors are described in U.S. Pat. Nos. 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and U.S. patent application Nos. 08/298,903, 08/298,650, 08/298,904 and 08/298,906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

Benzoxazin organic peroxyacid precursors

Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: ##STR5## wherein R₁ is H, alkyl, alkaryl, aryl, or arylalkyl. Preformed organic peroxyacid

The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: ##STR6## wherein R¹ is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R² is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.

Organic peroxyacid bleach release kinetics

In a preferred aspect, a means is provided for delaying the release to a wash solution of the organic peroxyacid bleach. The means may provide for delayed release of an organic peroxyacid bleach source itself to the wash solution. Alternatively, where the organic peroxyacid source is a peroxyacid precursor compound the delayed release means may comprise a means of inhibiting, or preventing the in situ perhydrolysis reaction which releases the organic peroxyacid into the solution. Such means could, for example, include delaying release of the hydrogen peroxide source to the wash solution, by for example, delaying release of any inorganic perhydrate salt, acting as a hydrogen peroxide source, to the wash solution.

The delayed release means can include coating any suitable component with a coating or mixture of coatings designed to provide the delayed release. The coating may therefore, for example, comprise a poorly water soluble material, or be a coating of sufficient thickness that the kinetics of dissolution of the thick coating provide the controlled rate of release.

The coating material may be applied using various methods. Any coating material is typically present at a weight ratio of coating material to bleach of from 1:99 to 1:2, preferably from 1:49 to 1:9.

Suitable coating materials include triglycerides (e.g. partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures thereof. Other suitable coating materials can comprise inorganic salts including the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate.

A preferred coating material is sodium silicate of SiO₂ : Na₂ O ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate. Magnesium silicate can also be included in the coating.

Any inorganic salt coating materials may be combined with organic binder materials to provide composite inorganic salt/organic binder coatings. Suitable binders include the C₁₀ -C₂₀ alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole of alcohol and more preferably the C₁₅ -C₂₀ primary alcohol ethoxylates containing from 20-100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 10,000 are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents. These polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C₁₀ -C₂₀ alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole. Further examples of binders include the C₁₀ -C₂₀ mono- and diglycerol ethers and also the C₁₀ -C₂₀ fatty acids.

Cellulose derivatives such as methylcellulose, carboxymethylcellulose, ethyl hydroxyethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts are other examples of binders suitable for use herein.

One method for applying the coating material involves agglomeration. Preferred agglomeration processes include the use of any of the organic binder materials described hereinabove. Any conventional agglomerator/mixer may be used including, but not limted to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.

Other means of providing the required delayed release include mechanical means for altering the physical characteristics of the bleach to control its solubility and rate of release. Suitable protocols could include compaction, mechanical injection, manual injection, and adjustment of the solubility of the bleach compound by selection of particle size of any particulate component.

Whilst the choice of particle size will depend both on the composition of the particulate component, and the desire to meet the desired delayed release kinetics, it is desirable that the particle size should be more than 500 micrometers, preferably having an average particle diameter of from 800 to 1200 micrometers.

Additional protocols for providing the means of delayed release include the suitable choice of any other components of the detergent composition matrix such that when the composition is introduced to the wash solution the ionic strength environment therein provided enables the required delayed release kinetics to be achieved.

Delayed release--kinetic parameters

The release of the organic peroxyacid bleach component is preferably such that in the T50 test method herein described the time to achieve a concentration that is 50% of the ultimate concentration of said peroxyacid bleach is more than 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds.

In a further preferred aspect of the invention the release of bleach is such that in the T50 test method herein described the time to achieve a level of total available oxygen (AvO) that is 50% of the ultimate level is more than 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds. A method for determining AvO levels is disclosed in European Patent Application No. 93870004.4.

In another preferred aspect of the invention, where the peroxyacid bleach source is a peroxyacid bleach precursor, employed in combination with a hydrogen peroxide source the kinetics of release to the wash solution of the hydrogen peroxide is such that the time to achieve a concentration that is 50% of the ultimate concentration of said hydrogen peroxide and said peroxyacid bleach precursor is more that 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds.

The ultimate wash concentration of any inorganic perhydrate bleach is typically from 0.005% to 0.25% by weight, but preferably is more than 0.05%, more preferably more than 0.075%.

The ultimate wash concentration of any peroxyacid precursor is typically 0.001% to 0.08% by weight, but preferably is from 0.005% to 0.05%, most preferably from 0.015% to 0.05%.

Delayed release--test method

The delayed release kinetics herein are defined with respect to a `T50 test method` which measures the time to achieve 50% of the ultimate concentration/level of that component when a composition containing the component is dissolved according to the standard conditions now set out.

The standard conditions involve a 1 liter glass beaker filled with 1000 ml of distilled water at 20° C., to which 10 g of composition is added. The contents of the beaker are agitated using a magnetic stirrer set at 100 rpm. The magnetic stirrer is pea/ovule-shaped having a maximum dimension of 1.5 cm and a minimum dimension of 0.5 cm. The ultimate concentration/level is taken to be the concentration/level attained 10 minutes after addition of the composition to the water-filled beaker.

Suitable analytical methods are chosen to enable a reliable determination of the incidental, and ultimate in solution concentrations of the component of concern, subsequent to the addition of the composition to the water in the beaker.

Such analytical methods can include those involving a continuous monitoring of the level of concentration of the component, including for example photometric and conductrimetric methods.

Alternatively, methods involving removing titres from the solution at set time intervals, stopping the disssolution process by an appropriate means such as by rapidly reducing the temperature of the titre, and then determining the concentration of the component in the titre by any means such as chemical titrimetric methods, can be employed.

Suitable graphical methods, including curve fitting methods, can be employed, where appropriate, to enable calculation of the the T50 value from raw analytical results.

The particular analytical method selected for determining the concentration of the component, will depend on the nature of that component, and of the nature of the composition containing that component.

Bleach catalyst

The compositions optionally contain a transition metal containing bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.

Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. No. 5,246,621 and U.S. Pat. No. 5,244,594. Preferred examples of these catalysts include Mn^(IV) ₂ (u--O)₃ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(PF₆)₂, Mn^(III) ₂ (u--O)₁ (u--OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(ClO₄)₂, Mn^(IV) ₄ (u--O)₆ (1,4,7-triazacyclononane)₄ -(ClO₄)₂, Mn^(III) Mn^(IV) ₄ (u--O)₁ (u--OAc)₂ -(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(ClO₄)₃, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

For examples of suitable bleach catalysts see U.S. Pat. No. 4,246,612 and U.S. Pat. No. 5,227,084. See also U.S. Pat. No. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH₃)₃ -(PF₆). Still another type of bleach catalyst, as disclosed in U.S. Pat. No. 5,114,606, is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C--OH groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N₄ Mn^(III) (u--O)₂ Mn^(IV) N₄)⁺ and [Bipy₂ Mn^(III) (u--O)₂ Mn^(IV) bipy₂ ]-(ClO₄)₃.

Further suitable bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. Pat. No. 4,728,455 (manganese/multidentate ligand catalyst), U.S. Pat. No. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. Pat. No. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. Pat. No. 4,626,373 (manganese/ligand catalyst), U.S. Pat. No. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. Pat. No. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. Pat. No. 4,728,455 (manganese gluconate catalysts).

It has been found that bleach catalysts, particularly Mn-containing bleach catalysts are of particular utility in detergent compositions containing high ratios of anionic to nonionic surfactants (e.g. 3:1 to 1:1) providing high levels of ionic strength to a wash solution (e.g. via the incorporation of high levels, for example greater than 15% by weight of the detergent composition, of citrate builder and/or sodium sulfate).

It has also been found that bleach catalysts, particularly Mn-containing bleach catalysts are of particular utility in detergent compositions containing high levels (e.g. >8% by weight of the detergent composition) of anionic surfactants and high levels (e.g. >5% by weight of the detergent composition) of organic polymeric compounds carrying anionic charge including for example, polycarboxylate and polyamino compounds.

It has further been found that bleach catalysts, particularly Mn-containing bleach catalysts are of particular utility in detergent compositions containing organic compounds with a cellulose backbone, such as cellulose ethers, including carboxymethyl cellulose.

Lime soap dispersant compound

The compositions of the invention may contain a lime soap dispersant compound, which has a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6. The lime soap dispersant compound is preferably present at a level of from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of the compositions.

A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. A numerical measure of the effectiveness of a lime soap dispersant is given by the lime soap dispersing power (LSDP) which is determined using the lime soap dispersion test as described in an article by H. C. Borghetty and C. A. Bergman, J. Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). This lime soap dispersion test method is widely used by practitioners in this art field being referred to , for example, in the following review articles; W. N. Linfield, Surfactant Science Series, Volume 7, p3; W. N. Linfield, Tenside Surf. Det. , Volume 27, pages 159-161, (1990); and M. K. Nagarajan, W. F. Masler, Cosmetics and Toiletries, Volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025 g of sodium oleate in 30 ml of water of 333 ppm CaCO₃ (Ca:Mg=3:2) equivalent hardness.

Surfactants having good lime soap dispersant capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.

Exemplary surfactants having a LSDP of no more than 8 for use in accord with the invention include C₁₆ -C₁₈ dimethyl amine oxide, C₁₂ -C₁₈ alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly C₁₂ -C₁₅ alkyl ethoxysulfate surfactant with a degree of ethoxylation of about 3 (LSDP=4), and the C₁₃ -C₁₅ ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the trade names Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.

Polymeric lime soap dispersants suitable for use herein are described in the article by M. K. Nagarajan and W. F. Masler, to be found in Cosmetics and Toiletries, Volume 104, pages 71-73, (1989). Examples of such polymeric lime soap dispersants include certain water-soluble salts of copolymers of acrylic acid, methacrylic acid or mixtures thereof, and an acrylamide or substituted acrylamide, where such polymers typically have a molecular weight of from 5,000 to 20,000.

Suds suppressing system

The detergent compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in U.S. Pat. No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and anmmonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈ -C₄₀ ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises

(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;

(c) an inert carrier fluid compound, most preferably comprising a C₁₆ -C₁₈ ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50° C. to 85° C., wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45° C. to 80° C.

Polymeric dye transfer inhibiting agents

The detergent compositions herein may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

a) Polyamine N-oxide polymers

Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula: ##STR7## wherein P is a polymerisable unit, and ##STR8## A is NC, CO, C, --O--, --S--, --N--; x is O or 1; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N--O group can be attached or wherein the nitrogen of the N--O group is part of these groups.

The N--O group can be represented by the following general structures ##STR9## wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N--O group can be attached or wherein the nitrogen of the N--O group forms part of these groups. The N--O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N--O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyarnine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N--O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N--O group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N--O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.

The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.

b) Copolymers of N-vinvlpyrrolidone and N-vinylimidazole

Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.

c) Polyvinylpyrrolidone

The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, N.Y. and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.

e) Polyvinvlimidazole

The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.

Optical brightener

The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful herein include those having the structural formula: ##STR10## wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Softening agents

Fabric softening agents can also be incorporated into laundry detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A-1 514 276 and EP-B-0 011 340.

Levels of smectite clay are normally in the range from 5% to 15%, more preferably from 8% to 12% by weight, with the material being added as a dry mixed component to the remainder of the formulation. Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight, whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.

Other optional ingredients

Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.

Form of the compositions

The detergent compositions of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids and gels. The compositions are preferably not in tablet-form. Most preferably, the compositions are in granular form.

Liquid compositions

The detergent compositions of the present invention may be formulated as liquid detergent compositions. Such liquid detergent compositions typically comprise from 94% to 35% by weight, preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight of a liquid carrier, e.g., water, preferably a mixture of water and organic solvent.

Gel compositions

The detergent compositions of the present invention may also be in the form of gels. Such compositions are typically formulated with polyakenyl polyether having a molecular weight of from about 750,000 to about 4,000,000.

Solid compositions

The detergent compositions of the invention are preferably in the form of solids, such as powders and granules. Granular form is preferred.

The particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.4 mm in diameter and not more than 5% of particles are less than 0.15 mm in diameter.

The bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 450 g/liter, more usually at least 600 g/liter and more preferably from 650 g/liter to 1200 g/liter.

Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrial cup disposed below the funnel. The funnel is 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement e.g. a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide the bulk density in g/liter. Replicate measurements are made as required.

Making processes--granular compositions

In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.

Washing methods

The compositions of the invention may be used in essentially any washing or cleaning method, including machine laundry and dishwashing methods.

Machine dishwashing method

A preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention. By an effective amount of the machine dishwashing composition it is typically meant from 8 g to 60 g of product dissolved or dispersed in a wash solution of volume from 3 to 10 liters, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.

Machine laundry methods

Machine laundry methods herein comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. The detergent can be added to the wash solution either via the dispenser drawer of the washing machine or by a dispensing device. By an effective amount of the detergent composition it is typically meant from 40 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 65 liters, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.

In a preferred washing method herein a dispensing device containing an effective amount of detergent product is introduced into the drum of a, preferably front-loading, washing machine before the commencement of the wash cycle.

The dispensing device is a container for the detergent product which is used to deliver the product directly into the drum of the washing machine. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its immersion in the wash water.

To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of components such as water-soluble builder and heavy metal ion sequestrant components in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle. Especially preferred dispensing devices for use in accord with the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette".

Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.

Abbreviations used in Examples

In the detergent compositions, the abbreviated component identifications have the following meanings:

LAS: Sodium linear C₁₂ alkyl benzene sulfonate

TAS: Sodium tallow alkyl sulfate

C45AS: Sodium C₁₄ -C₁₅ linear alkyl sulfate

CxyEzS: Sodium C_(1x-C) _(1y) branched alkyl sulfate condensed with z moles of ethylene oxide

CxyEz: A C_(1x-1y) predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide

QAS: R₂.N⁺ (CH₃)₂ (C₂ H₄ OH) with R₂ =C₁₂ -C₁₄

Soap: Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.

TFAA: C₁₆ -C₁₈ alkyl N-methyl glucamide

TPKFA: C₁₂ -C₁₄ topped whole cut fatty acids

STPP: Anhydrous sodium tripolyphosphate

Zeolite A: Hydrated Sodium Aluminosilicate of formula Na₁₂ (A10₂ SiO₂)₁₂. 27H₂ O having a primary particle size in the range from 0.1 to 10 micrometers

NaSKS-6: Crystalline layered silicate of formula δ-Na₂ Si₂ O₅

Citric acid: Anhydrous citric acid

Carbonate: Anhydrous sodium carbonate with a particle size between 200 μm and 900 μm

Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400 μm and 1200 μm

Silicate: Amorphous Sodium Silicate (SiO₂ :Na₂ O; 2.0 ratio)

Sodium sulfate: Anhydrous sodium sulfate

Citrate: Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425 μm and 850 μm

MA/AA: Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000.

CMC: Sodium carboxymethyl cellulose

Protease: Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tradename Savinase

Alcalase: Proteolytic enzyme of activity 3AU/g sold by NOVO Industries A/S

Cellulase: Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename Carezyme

Amylase: Amylolytic enzyme of activity 120 KNU/g sold by NOVO Industries A/S under the tradename Termamyl 120T

Lipase: Lipolytic enzyme of activity 100kLU/g sold by NOVO Industries A/S under the tradename Lipolase

Endolase: Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S

PB4: Sodium perborate tetrahydrate of nominal formula NaBO₂.3H₂ O.H₂ O₂

PB1: Anhydrous sodium perborate bleach of nominal formula NaBO₂.H₂ O₂

Percarbonate: Sodium Percarbonate of nominal formula 2Na₂ CO₃.3H₂ O₂

NOBS: Nonanoyloxybenzene sulfonate in the form of the sodium salt.

TAED: Tetraacetylethylenediamine

DTPMP: Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060

Photoactivated: Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer

Brightener 1: Disodium 4,4'-bis(2-sulphostyryl)biphenyl

Brightener 2: Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate.

HEDP 1,1-hydroxyethane diphosphonic acid PVNO Polyvinylpyridine N-oxide

PVPVI: Copolymer of polyvinylpyrolidone and vinylimidazole

SRP 1: Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone

SRP 2: Diethoxylated poly (1,2 propylene terephtalate) short block polymer

Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.

In the following Examples all levels are quoted as % by weight of the composition. Levels of aluminosilicate builder in the Examples are expressed on an active basis.

EXAMPLE 1

The following laundry detergent compositions A to F were prepared. B to F are in accord with the invention, A is a comparative composition. The T50 value for release of peracetic acid to a wash solution measured according to the T50 test method protocol described herein is greater than 180 seconds for each of compositions A to F.

    ______________________________________                                                A     B       C       D     E     F                                     ______________________________________                                         LAS      7.5     7.5     8.0   8.0   8.0   8.0                                 68AS     1.5     1.5     --    --    --    --                                  C24E5    5.0     5.0     --    --    --    --                                  C25E3    --      --      3.4   3.4   3.4   3.4                                 QAS      --      --      --    --    0.8   --                                  Zeolite A                                                                               18.85   13.25   13.1  13.1  13.1  13.1                                NaSKS-6/citric                                                                          --      5.6     5.6   5.6   5.6   5.6                                 acid (79:21)                                                                   Carbonate                                                                               20.0    20.0    13.0  27.0  27.0  27.0                                Silicate 2.0     2.0     1.4   3.0   3.0   3.0                                 Sodium sulfate                                                                          15.3    15.3    16.1  26.1  26.1  26.1                                PB4      16.0    16.0    9.0   9.0   9.0   9.0                                 TAED     1.5     1.5     1.5   1.5   1.5   1.5                                 EDDS      0.25    0.21   --    --    --    --                                  DETPMP   --      --       0.25  0.25  0.25  0.25                               HEDP      0.22    0.22   0.3   0.3   0.3   0.3                                 Protease 0.6     0.6      0.26  0.26  0.26  0.26                               Amylase  0.4     0.4     0.6   0.5   0.4   0.3                                 MA/AA    1.8      2.15   0.3   0.8   0.5   0.3                                 CMC      0.6     0.6     0.2   0.2   0.2   0.2                                 Photoactivated                                                                          15      15      15    15    15    15                                  bleach (ppm)                                                                            ppm     ppm     ppm   ppm   ppm   ppm                                 Brightener 1                                                                             0.12    0.12    0.09  0.09  0.09  0.09                               Perfume   0.22    0.22   0.3   0.3   0.3   0.3                                 Silicone 0.0.8    0.08   0.5   0.5   0.5   0.5                                 antifoam                                                                       Misc/minors to                                                                 100%                                                                           Density in                                                                              700     700     850   850   850   850                                 g/liter                                                                        ______________________________________                                    

Comparative Performance Testing

Test protocol--stain removal

Two white cotton sheets were prewashed in a non-biological bleach-free heavy duty detergent. Stains were then evenly applied to the cotton sheet, in strips 2 cm wide, using a paint brush. Chocolate-flavoured porridge stains were applied to the first sheet and chocolate pudding stains, to the second one. Chocolate-containing stains are known to be enzyme sensitive. Sets of test swatches of size 6 cm×6 cm were cut from each sheet.

The sets of fabric swatches were subjected to one wash cycle in an automatic washing machine, using as the detergent either Composition A or B. This wash procedure was repeated for eight sets of swatches, each prepared as above.

In more detail, a Miele 820 automatic washing machine was employed, and the 20° C. short cycle programme selected. Water of 12° Clark hardness (=1.8 mmol Ca²⁺ /liter) was used. 140 g of detergent, dispensed through the drawer, was employed. One swatch of each stain type was washed along with a ballast load comprising 2.0 Kg of a 60/40 mixture of lightly soiled synthetic and cotton fabrics. The ballast load was positioned prior to commencement of the wash cycle to ensure an even distribution around the test swatch.

All of the swatches were then assessed for removal of the two chocolate-containing stains by a four person grading panel using the well-known four-point Scheffe scale, and the results for the eight comparisons were averaged.

Comparative testing--results

The above stain removal test protocol was followed in comparing the efficiency of Compositions A and B in removing the named stains.

The results (in PSU) obtained were as follows:

    ______________________________________                                                           A   B                                                        ______________________________________                                         Chocolate-flavoured ref   +0.8                                                 porridge stains                                                                Chocolate pudding   ref   +0.5                                                 stains                                                                         ______________________________________                                    

The stain removal performance of Composition B on chocolate-based stains is thus shown to be enhanced in comparison to that of Composition A, in accord with the invention.

EXAMPLE 2

The following granular laundry detergent compositions G to I of bulk density 750 g/liter were prepared in accord with the invention:

    ______________________________________                                                     G        H       I                                                 ______________________________________                                         LAS            5.25       5.61    4.76                                         TAS            1.25       1.86    1.57                                         C45AS         --          2.24    3.89                                         C2SAE3S       --          0.76    1.18                                         C45E7          3.25      --      5.0                                           C25E3         --         5.5     --                                            QAS           0.8        2.0     2.0                                           Zeolite A     19.5       19.5    19.5                                          NaSKS-6/citric acid                                                                          10.6       10.6    10.6                                          (79:21)                                                                        Carbonate     12.1       21.4    21.4                                          Bicarbonate   --         2.0     2.0                                           Silicate      6.8        --      --                                            Sodium sulfate                                                                               25.8       --      14.3                                          PB4           5.0        12.7    --                                            TAED          0.5        3.1     --                                            DETPMP         0.25      0.2     0.2                                           HEDP          --         0.3     0.3                                           Protease       0.26       0.85    0.85                                         Lipase         0.15       0.15    0.15                                         Cellulase      0.28       0.28    0.28                                         Amylase       0.6        0.8     0.8                                           MA/AA         0.8        1.6     1.6                                           CMC           0.2        0.4     0.4                                           Photoactivated bleach                                                                        15 ppm     27 ppm  27 ppm                                        (ppm)                                                                          Brightener 1   0.08       0.19    0.19                                         Brightener 2  --          0.04    0.04                                         Perfume       0.3        0.3     0.3                                           Silicone antifoam                                                                            0.5        2.4     2.4                                           Minors/misc to 100%                                                            ______________________________________                                    

EXAMPLE 3

The following detergent formulations according to the present invention were prepared:

    ______________________________________                                                     J        K       L                                                 ______________________________________                                         Blown Powder                                                                   Zeolite A     24.0       24.0    24.0                                          C45AS         9.0        6.0     13.0                                          MA/AA         2.0        4.0     2.0                                           LAS           6.0        8.0     11.0                                          TAS           2.0        --      --                                            Silicate      7.0        3.0     3.0                                           CMC           1.0        1.0     0.5                                           Brightener 2  0.2        0.2     0.2                                           Soap          1.0        1.0     1.0                                           DTPMP         0.4        0.4     0.2                                           Spray On                                                                       C45E7         2.5        2.5     2.0                                           C25E3         2.5        2.5     2.0                                           Silicone antifoam                                                                            0.3        0.3     0.3                                           Perfume       0.3        0.3     0.3                                           Dry additives                                                                  Carbonate     3.0        7.0     7.0                                           NaSKS-6/citric acid                                                                          4.0        6.0     8.0                                           (79:21)                                                                        PB4           18.0       18.0    10.0                                          PB1           4.0        4.0     0                                             TAED          3.0        3.0     1.0                                           Photoactivated bleach                                                                         0.02       0.02    0.02                                         Protease      1.0        1.0     1.0                                           Lipase        0.4        0.4     0.4                                           Amylase       0.2        0.5     0.6                                           Dry mixed sodium                                                                             3.0        3.0     5.0                                           sulfate                                                                        Balance (Moisture &                                                                          100.0      100.0   100.0                                         Miscellaneous)                                                                 Density (g/liter)                                                                            630        670     670                                           ______________________________________                                    

EXAMPLE 4

The following nil bleach-containing detergent formulations of particular use in the washing of colored clothing, according to the present invention were prepared:

    ______________________________________                                                     M        N       O                                                 ______________________________________                                         Blown Powder                                                                   Zeolite A     15.0       15.0    --                                            Sodium sulfate                                                                               0.0        5.0     --                                            LAS           3.0        3.0     --                                            DTPMP         0.4        0.5     --                                            CMC           0.4        0.4     --                                            MA/AA         4.0        4.0     --                                            Agglomerates                                                                   C45AS         --         --      11.0                                          LAS           6.0        5.0     --                                            TAS           3.0        2.0     --                                            Silicate      2.0        2.0     --                                            Zeolite A     10.0       10.0    13.0                                          CMC           --         --      0.5                                           MA/AA         --         --      2.0                                           Carbonate     5.0        5.0     7.0                                           Spray On                                                                       Perfume       0.3        0.3     0.5                                           C45E7         4.0        4.0     4.0                                           C25E3         2.0        2.0     2.0                                           Dry additives                                                                  MA/AA         --         --      3.0                                           NaSKS-6       8.0        8.0     12.0                                          Citrate       4.0        4.0     8.0                                           Bicarbonate   2.0        1.0     5.0                                           Carbonate     6.0        4.0     7.0                                           PVPVI/PVNO    0.5        0.5     0.5                                           Alcalase      0.5        0.3     0.9                                           Lipase        0.4        0.4     0.4                                           Amylase       0.6        0.6     0.6                                           Cellulase     0.6        0.6     0.6                                           Silicone antifoam                                                                            5.0        5.0     5.0                                           Dry additives                                                                  Sodium sulfate                                                                               0.0        9.0     0.0                                           Balance (Moisture and                                                                        100.0      100.0   100.0                                         Miscellaneous)                                                                 Density (g/liter)                                                                            700        700     700                                           ______________________________________                                    

EXAMPLE 5

The following detergent formulations, according to the present invention were prepared:

    ______________________________________                                                     P         Q      R                                                 ______________________________________                                         Blown Powder                                                                   Zeolite A     20.0        16.0   6.0                                           Sodium sulfate                                                                               19.0        5.0    7.0                                           MA/AA         3.0         3.0    6.0                                           LAS           14.0        12.0   22.0                                          C45AS         8.0         7.0    7.0                                           Silicate      --          1.0    5.0                                           Soap          --          --     2.0                                           Brightener 1  0.2         0.2    0.2                                           Carbonate     8.0         16.0   15.0                                          DTPMP         --          0.4    0.4                                           Spray On                                                                       C45E7         1.0         1.0    1.0                                           Dry additives                                                                  PVPVI/PVNO    0.5         0.5    0.5                                           Protease      1.0         1.0    1.0                                           Lipase        0.4         0.4    0.4                                           Amylase       0.4         0.4    0.4                                           Cellulase     0.1         0.1    0.1                                           NaSKS-6/citric acid                                                                          6.0         8.0    6.0                                           (79:21)                                                                        NOBS          --          6.1    4.5                                           PB1           1.0         5.0    6.0                                           Sodium sulfate                                                                               --          6.0    --                                            Balance (Moisture                                                                            100         100    100                                           and Miscellaneous)                                                             ______________________________________                                    

EXAMPLE 6

The following high density and bleach-containing detergent formulations, according to the present invention were prepared:

    ______________________________________                                                       S        T       U                                               ______________________________________                                         Blown Powder                                                                   Zeolite A       15.0       15.0    15.0                                        Sodium sulfate  0.0        5.0     0.0                                         LAS             3.0        3.0     3.0                                         QAS             --         1.5     1.5                                         DTPMP           0.4        0.4     0.4                                         CMC             0.4        0.4     0.4                                         MA/AA           4.0        2.0     2.0                                         Agglomerates                                                                   LAS             5.0        5.0     5.0                                         TAS             2.0        2.0     1.0                                         Silicate        3.0        3.0     4.0                                         Zeolite A       8.0        8.0     8.0                                         Carbonate       8.0        8.0     4.0                                         Spray On                                                                       Perfume         0.3        0.3     0.3                                         C45E7           2.0        2.0     2.0                                         C25E3           2.0        --      --                                          Dry additives                                                                  Citrate         5.0        --      2.0                                         Bicarbonate     --         3.0     --                                          NaSKS-6/citric acid (79:21)                                                                    6.0        8.0     6.0                                         Carbonate       2.0        7.0     4.0                                         TAED            6.0        2.0     5.0                                         PB1             14.0       7.0     10.0                                        Polyethylene oxide of MW                                                                       --         --      0.2                                         5,000,000                                                                      Bentonite clay  --         --      10.0                                        Protease        1.0        1.0     1.0                                         Lipase          0.4        0.4     0.4                                         Amylase         0.4        0.6     0.4                                         Cellulase       0.6        0.6     0.6                                         Silicone antifoam                                                                              5.0        5.0     5.0                                         Dry additives                                                                  Sodium sulfate  0.0        3.0     0.0                                         Balance (Moisture and                                                                          100.0      100.0   100.0                                       Miscellaneous)                                                                 Density (g/liter)                                                                              850        850     850                                         ______________________________________                                    

EXAMPLE 7

The following high density detergent formulations, according to the present invention were prepared:

    ______________________________________                                                          V     W                                                       ______________________________________                                         Agglomerate                                                                    C45AS              11.0    14.0                                                Zeolite A          15.0    6.0                                                 Carbonate          4.0     8.0                                                 MA/AA              4.0     2.0                                                 CMC                0.5     0.5                                                 DTPMP              0.4     0.4                                                 Spray On                                                                       C25E5              5.0     5.0                                                 Perfume            0.5     0.5                                                 Dry Adds                                                                       HEDP               0.5     0.3                                                 SKS 6              13.0    10.0                                                Citrate            3.0     1.0                                                 TAED               5.0     7.0                                                 Percarbonate       20.0    20.0                                                SRP 1              0.3     0.3                                                 Protease           1.4     1.4                                                 Lipase             0.4     0.4                                                 Cellulase          0.6     0.6                                                 Amylase            1.0     0.8                                                 Silicone antifoam  5.0     5.0                                                 Brightener 1       0.2     0.2                                                 Brightener 2       0.2     --                                                  Balance (Moisture and                                                                             100     100                                                 Miscellaneous)                                                                 Density (g/liter)  850     850                                                 ______________________________________                                     

What is claimed is:
 1. A detergent composition containing(a) an amylase enzyme; and (b) a builder system comprising(i) an aluminosilicate zeolite; and (ii) a crystalline layered silicate wherein the weight ratio of said crystalline layered silicate to said amylase enzyme (120 KNU/gram activity basis) is from 7:1 to 20:1 and (c) a surfactant mixture comprising an alkyl benzene sulfonate, alkyl sulfate, and an alcohol ethoxylate wherein said detergent composition has an improved ability to remove chocolate-based stains from the substrate being cleaned surfactant.
 2. A detergent composition according to claim 1 wherein said amylase enzyme is an an α-amylase.
 3. A detergent composition according to claim 1 wherein the amylase enzyme is present at a level of from 0.2% to 3% by weight (120 KNU/g activity basis) of the composition.
 4. A detergent composition according to claim 1 wherein the weight ratio of the crystalline layered silicate to the amylase enzyme (120 KNU/gram activity basis) is from 8:1 to 18:1.
 5. A detergent composition according to claim 1 wherein said aluminosilicate zeolite is present at a level of from 40% to 98%, active aluminosilicate zeolite by weight of the builder system.
 6. A detergent composition according to claim 1 wherein the crystalline layered silicate has the general formula

    NaMSi.sub.x O.sub.2x+1.yH.sub.2 O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to
 20. 7. A detergent composition according to claim 1 wherein the crystalline layered silicate is present at a level of from 1% to 35% crystalline layered silicate by weight of the builder system.
 8. A detergent composition according to claim 1 wherein said builder system additionally contains an organic polymeric compound.
 9. A detergent composition according to claim 8 wherein said organic polymeric compound contains acrylic acid monomer units.
 10. A detergent composition according to claim 8 wherein the organic polymeric compound is present at a level of from 0.1% to 20% organic polymeric compound by weight of the builder system.
 11. A detergent composition according to claim 1 which is in granular form.
 12. A detergent composition according to claim 1 manufactured by combining an amylase enzyme and a builder system comprising an aluminosilicate zeolite and a crystalline layered silicate, wherein the weight ratio said crystalline layered silicate to said amylase enzyme (12 KNU/gram activity basis) is from 7:1 to 20:1. 